EP2593529A1 - Fluides cristallins liquides et écrans à cristaux liquides à orientation homéotrope à stabilisation polymère - Google Patents

Fluides cristallins liquides et écrans à cristaux liquides à orientation homéotrope à stabilisation polymère

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Publication number
EP2593529A1
EP2593529A1 EP11735985.1A EP11735985A EP2593529A1 EP 2593529 A1 EP2593529 A1 EP 2593529A1 EP 11735985 A EP11735985 A EP 11735985A EP 2593529 A1 EP2593529 A1 EP 2593529A1
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Prior art keywords
component
atoms
group
independently
particles
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EP11735985.1A
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German (de)
English (en)
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EP2593529B1 (fr
Inventor
Graziano Archetti
Andreas Taugerbeck
Renate Bender
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • Liquid-crystalline media and liquid crystal displays with polymer-stabilized homeotropic alignment Liquid-crystalline media and liquid crystal displays with polymer-stabilized homeotropic alignment
  • the present invention relates to liquid-crystalline media and liquid crystal displays (FK displays) containing this polymer-stabilized, homeotropic (vertical) alignment of the liquid-crystalline medium (FK medium).
  • the FK medium according to the invention contains particles with a mass of at least 450 Da, which by a polar, organic
  • Anchor group are functionalized.
  • VAN Very Aligned Nematic
  • ASV Advanced Super View, eg: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Lecture 15.2: “Development of High Quality LCDTV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754 to 757) Advertisements, besides IPS (In Plane switching) (eg: Yeo, SD, Lecture 15.3: "A LC Display for the TV Application", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 758 & 759) and the long known TN (Twisted Nematic) ads, as one of the three most important newer types of
  • Liquid crystal displays especially for television applications, established.
  • the technologies are e.g. in Souk, Jun,
  • Substrate surfaces and physical influences such as heat, radiation in the infrared, visible and ultraviolet range and electrical alternating and alternating fields.
  • LC phases require a liquid-crystalline mesophase in a suitable temperature range and a low viscosity.
  • Matrix liquid crystal displays are known.
  • active elements i.e., transistors
  • non-linear elements for individual switching of the individual pixels.
  • active matrix whereby one can distinguish two types:
  • MOS Metal Oxide Semiconductor
  • TFT Thin-film transistors
  • Type 1 typically uses dynamic scattering or guest-host effect as the electro-optic effect.
  • the use of monocrystalline silicon as a substrate material limits the display size, since the modular composition of various partial displays on the joints leads to problems.
  • the TN effect is usually used as the electro-optical effect.
  • TFTs made of compound semiconductors, such as e.g. CdSe or TFTs based on polycrystalline or amorphous silicon.
  • CdSe compound semiconductors
  • TFTs based on polycrystalline or amorphous silicon The latter technology is being worked on worldwide with great intensity.
  • the TFT matrix is applied on the inside of one glass plate of the display, while the other glass plate on the inside carries the transparent counter electrode. Compared to the size of the pixel electrode, the TFT is very small and practically does not disturb the image.
  • This technology can also be extended to fully color-capable image representations, wherein a mosaic of red, green and blue filters is arranged such that each one filter element is opposite to a switchable image element.
  • MFK displays here includes any matrix display with integrated nonlinear elements, i.
  • Such MFK displays are particularly suitable for TV applications (eg pocket TV) or for high-information displays in automotive or aircraft.
  • difficulties arise with MFK displays due to a not sufficiently high specific Resistance of liquid crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, p. 141 ff, Paris; STROMER, M., Proc. Eurodisplay 84, Sept. 1984: Design of Thin Film Transistors for Matrix Liquid Crystal Displays, p. 145 ff, Paris]. With decreasing resistance, the contrast of one deteriorates
  • VA ads are generally meant to have a very high specific
  • a polyimide layer on the substrate surfaces ensures the homeotropic orientation of the liquid crystal.
  • the preparation of a suitable orientation layer in the display requires considerable effort.
  • interactions of the orientation layer with the FK medium can degrade the electrical resistance of the VA display. Because of such possible interactions, the number of suitable liquid crystal components is significantly reduced. Therefore, it would be desirable to achieve the homeotropic alignment of the FK medium without polyimide.
  • the drawback of the commonly used MFK TN displays is their relatively low contrast, the relatively high viewing angle dependence, and the difficulty in creating grayscale in these displays. Significantly better viewing angle dependencies are found on VA displays and are therefore mainly used for TVs and monitors.
  • PSA displays (“Polymer Sustained” or “Polymer Sustained Alignment”), for which occasionally the term “Polymer Stabilized” is used.
  • FK medium will have a small amount (for example 0.3% by weight, typically ⁇ 1% by weight) of one or more polymerisable
  • PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN displays are known.
  • the polymerization of the polymerizable compound (s) is carried out in PSA-VA and PSA-OCB displays, preferably with applied electrical voltage, in PSA-IPS displays with or without applied electrical voltage.
  • the PS (A) method results in a 'pretilt' in the cell.
  • PSA-OCB displays for example, one can achieve that the Bend structure is stabilized, so that one can do without or reduce offset voltage.
  • the 'pretilt' has a positive effect on the switching times.
  • PSA-VA displays a standard MVA or PVA pixel and electrode layout can be used. In addition, but you can also, for example, with only a structured electrode side and without Protrusions get along, which significantly simplifies the production and at the same time leads to a very good contrast with very good light transmission.
  • PSA-VA displays are described, for example, in JP 10-036847 A, EP 1 170 626 A2, US Pat. Nos. 6,861,107, 7,169,449, US 2004/0191428 A1, US 2006/0066793 A1 and US 2006/0103804 A1.
  • PSA-OCB displays are described, for example, in T.J. Chen et al., Jpn. J. Appl. Phys. 45, 2006, 2702-2704 and S.H. Kim, L.-C-Chien, Jpn. J. Appl. Phys. 43, 2004, 7643-7647.
  • PSA IPS displays are described, for example, in US 6,177,972 and Appl. Phys. Lett. 1999, 75 (21), 3264.
  • PSA TN displays are described, for example, in Optics Express 2004, 12 (7), 1221.
  • PSA displays like the conventional FK displays described above, can be operated as active matrix or passive matrix displays.
  • active matrix displays the control of individual pixels is usually done by integrated, non-linear active elements such as
  • transistors e.g., thin film transistors, or TFTs
  • passive matrix displays both of which are known in the art.
  • polymerizable compounds of the following formula are used for PSA-VA wherein P represents a polymerizable group, usually an acrylate or methacrylate group, as for example in US 7,169,449
  • the switching time of a VA display depends to a large extent on the setting of the 'pretilts'.
  • the overhead including generating a
  • JP 2010170090 A discloses a dendrimer in addition to liquid-crystal mixtures which effects vertical alignment with respect to substrates.
  • a passivation layer is also particularly important because the polyimide layer not only provides orientation of the LC medium but also provides electrical isolation. Without a passivation layer, reliability issues such as R-DC ('Residual DC') may appear.
  • a conference poster on SID 2010 (H.Y. Gim et al., P-128) discloses that a phenethyl-substituted polyhedral oligomeric silsesquioxane is used at a concentration of 10% by weight in a display without a conventional PS-VA type orientation layer.
  • the FK medium is homeotropically oriented by the PSS.
  • the large amount of dopant significantly affects the properties of the FK medium, so the number of liquid crystal components that can be used for such FK display is very limited.
  • An object of the present invention is a FK medium containing a low molecular weight liquid crystalline component having a negative dielectric anisotropy of the value ⁇ ⁇ -1.5, containing a polymerized or polymerizable component and a component (N)
  • Another object of the present invention is a
  • Liquid crystal display comprising a liquid crystal cell (FK cell) with two substrates and two electrodes, wherein at least one substrate is transparent and at least one substrate has one or two electrodes, as well as a between the substrates located layer of a liquid crystal medium (FK medium ) comprising a low molecular weight liquid crystalline component having a negative dielectric anisotropy of ⁇ ⁇ -1.5, a polymerized or polymerizable component and a component (N) as defined above and below which is capable of forming a homeotropic (vertical)
  • the polymerized component is obtainable by polymerization of one or more polymerizable compounds between the substrates of the FK cell in LC medium, optionally with application of an electrical voltage to the electrodes of the cell.
  • Another object of the invention is a method for producing a FK display, preferably of the PSA-VA type, comprising a FK cell having two substrates and two electrodes, wherein at least one substrate is transparent and at least one substrate has one or two electrodes comprising the method steps:
  • the component (N) is dissolved or dispersed in the liquid crystal. It causes a homeotropic alignment of the liquid crystal with respect to the substrate surfaces. It comprises particles with a mass of at least 450 Da, the particles having one or more organic polar atoms
  • Anchor groups include, preferably in a proportion of 50, 75, 90
  • component (N) consists entirely of such particles.
  • the mass of the particles is preferably 600 Da or more, and 2000 Da or less.
  • Component (N) should be chemically inert, non-aging, and preferably lipophilic, to be compatible and soluble or dispersible in contact with LC media. Suitable particles of component (N) are, for example
  • Silsesquioxane compounds with a polar anchor group which can be considered both as chemical compounds and as nanoparticles of about 1-5 nm size.
  • other large molecule residues are also used as particles, which defines a molecular one
  • the particles may be organic molecules or organic / inorganic hybrid particles.
  • the inorganic part may have a molecularly defined structure (eg, PSS), or may be an accumulation of lower order atoms (clusters, metal nanoparticles, nanocrystals, etc.).
  • the particles of component (N) have a diameter greater than or equal to 1 nm, preferably a diameter of 1 to 5 nm. It is preferred that the particles of component (N) have an aspect ratio dmax dmin of at most 3: 1, preferably 2: 1, own. D max denotes the maximum length expansion and d m m the minimum
  • Length extension of a nonspherical particle For rod-shaped particles d max denotes the length, and d min the width or the smallest diameter. For platelet-shaped particles d max denotes the
  • Diameter and d m i n the thickness.
  • the maximum elongation should preferably be 1 nm or more, preferably 1-5 nm.
  • the average diameter is used on the assumption that the particle is approximately spherical. In this case, the average diameter should be used instead of the largest length dimension. The same applies to statistical size distributions.
  • the size relationships of molecular structures can be determined with the help of simple models or calculations of the
  • Bond lengths and Van der Waals radii of the participating atoms assumes.
  • the size and shape of other nanoparticulate materials can be determined by scattering methods in solution or transmission electron microscopy (TEM).
  • the particles of component (N) are preferably in one
  • Component (N) usually leads to completely homeotropic orientation of the FK layer at the usual cell thicknesses (3 to 4 pm).
  • the anchor group of component (N) preferably consists of a group which has a non-covalent interaction with the substrate surface Glass or metal oxides.
  • Suitable groups are polar groups comprising groups having atoms selected from N, O, S, and P, which are sufficiently stable at the same time.
  • one or more, preferably two or more, of these heteroatoms are included in the anchor group.
  • the anchor group particularly preferably consists of at least two structural elements containing heteroatoms selected from (N, O), and covalent, linking structures between the heteroatoms and between one or more of the heteroatoms and the rest of the
  • Structures consist of chain-like or cyclic aliphatic radicals and / or aromatic rings, preferably of saturated
  • Aromatic rings include e.g. Cyclohexane and cyclopentane. Aromatic rings preferably include benzene, e.g. 1, 4, 1, 3 or 1,2-phenylene.
  • a preferred component (N) is characterized in that the
  • Compounds or particles of component (N) by an anchor comprising at least one, two or more primary or secondary amine functions (tert-N, -NH-, -NH 2 ), ether groups (-O-) or
  • Hydroxy groups (-OH) is functionalized.
  • two hetero-functions are preferably arranged relative to one another in such a way that they interact with an atom of a binding partner in the manner of a two- or three-membered molecule can accommodate multidentate chelate ligands.
  • the nature and position of the amino functions corresponds to those of an ethylenediamine (-NH-CH 2 CH 2 -NH 2 ).
  • Particles of component (N) in a preferred embodiment have the general formula
  • a * means the polar anchor group
  • O represents the remaining particle without the anchor group.
  • Particle O essentially determines the size of the particle and, as a rule, the majority of the mass.
  • the anchor group A * preferably denotes a group of the formula
  • Sp is a single bond or a spacer group such as a sp
  • X 1 is a group -NH 2 , -NHR 1 -NR 1 2 , -CN, -OR or -OH, - (CO) OH, or a group of the formulas
  • R 0 is H or alkyl of 1 to 12 C atoms
  • X 2 are each independently -NH-, -NR 1 -, -O- or a single bond
  • Z 2 are each independently an alkylene group having 1-15 C atoms, carbocyclic rings having 5 or 6 C atoms (eg optionally substituted benzene, cyclohexane), or combinations of one or more rings and alkylene groups, wherein in each case one or more hydrogen atoms by OH, OR 1 , -NH 2 , -NHR 1 -, -NR 1 2 , or halogen (preferably F, Cl) may be replaced.
  • R 1 are each independently a halogenated or unsubstituted
  • the anchor group consists of this radical and means A * .
  • the anchor group of component (N) particularly preferably comprises a (N / O) heteroatom-containing radical of sub-formula (A2)
  • anchor group consists of this radical and means A * .
  • Particularly preferred nitrogen-containing anchor groups A * are selected from
  • n, n1, n2 and n3 are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, in particular 1, 2, 3 or 4.
  • the multiple heteroatom (N, O) groups possess special strength
  • Anker group They can be used in smaller concentrations.
  • nitrogen-free anchor groups A * are selected from -OH, - (CH 2) n -OH, -O- (CH 2) n -OH, - [O- (CH 2) n1 -] n2-OH, - (CO )OH,
  • n, n1 and n2 is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, in particular 1, 2, 3 or 4. These are very compatible with liquid crystalline media.
  • the particles used may be the same or different from each other. You can either go through the molecular structure
  • Nanoparticles or by isotope distributions are Nanoparticles or by isotope distributions.
  • a particle has exactly one anchor group.
  • anchor groups are not excluded.
  • parent particles having multiple anchor groups are formed. Examples of this type are dimers or oligomers of polyhedrals
  • Silsesquioxanes functionalized on each PSS unit by an anchor group The merger of several PSS cores takes place via the attached to the corners of organic radicals.
  • the PSS core can also be broken open and even have several OH groups as an anchor (compare PSS-7 below).
  • Preferred particles of component (N) have a polar anchor group, but are at the surface of the particle by hydrocarbon radicals, preferably by
  • Preferred particles which are silsesquioxanes have the general structure PSS-0:
  • a * is an anchor group as described above and below, and each R 4 is independently an optionally halogenated one
  • Hydrocarbon radical preferably an unfunctionalized or halogenated aliphatic radical, an aromatic radical (in particular benzene radical) or combinations thereof,
  • an alkyl radical or an alkenyl radical having in each case up to 15 C atoms, which is optionally monosubstituted or polysubstituted by phenyl and / or halogen,
  • Particularly preferred particles as component (N) are selected from the following exemplified compounds which are preferred
  • component (N) particles are used which, as further functionalization, have one or more polymerisable groups in addition to the polar anchor (compare group P a or P b below).
  • polymerizable groups are groups such as acrylate, methacrylate,
  • Fluoroacrylate, oxetane, vinyloxy or epoxy group more preferably acrylate and methacrylate.
  • component (N) in the polymerization permanently immobilizes the nanoparticles, thereby maintaining their function.
  • An advantage of the FK displays according to the invention is that the display achieves the desired homeotropic orientation without the usual polyimide alignment layer. Due to the polymer stabilization this remains
  • the displays of the invention are characterized by improved
  • Component can simultaneously serve as a passivation layer, which increases the reliability (the so-called 'reliability') of the display.
  • the small amount of component (N) affects the properties of the LC media practically negligible, therefore, a wide variety of liquid crystal components can be used in the LC display.
  • the FK displays according to the invention therefore preferably have no alignment layer for homeotropic alignment on the surfaces of the FK cell.
  • the FK displays according to the invention use an FK medium with negative dielectric anisotropy ( ⁇ ⁇ -1.5). In general, this is a VA display with electrodes arranged on opposite sides of the FK cell.
  • the FK displays are provided in the usual way with polarizer (s), which make the switching process of the FK medium visible.
  • the polymerized component of the FK cell is obtainable by polymerizing a polymerizable component (monomers).
  • the monomers are first dissolved in the LC medium and are polymerized in the LC cell after a homeotropic orientation or a high tilt angle of the LC medium has been established.
  • a voltage can be applied to the FK cell. In the simplest case, such a tension is unnecessary and the desired orientation is determined solely by the nature of the medium and the cell geometry.
  • the suitable monomers (polymerisable component) of the LC medium are those of the prior art which are used for PSA-VA displays, in particular polymerizable compounds of formula II below and / or of the formulas M1 to M22.
  • the LC media according to the invention for use in PSA ads preferably comprise ⁇ 5% by weight, more preferably ⁇ 1% by weight and very preferably ⁇ 0.5% by weight of polymerisable
  • Suitable monomers of the polymerizable component of the LC medium are described by the following formula II: in which the individual radicals have the following meaning:
  • P a , P b are each independently a polymerizable group
  • a 1 , A 2 each independently a radical selected from the following groups a) the group consisting of trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene and 4,4 ' bicyclohexylene, wherein also one or more non-adjacent CH 2 groups may be replaced by -O- and / or -S- and in which one or more H atoms may be replaced by F, b) the group consisting of 1, 4-phenylene and 1, 3-phenylene, wherein also one or two CH groups may be replaced by N and in which also one or more H atoms may be replaced by L, c) the group consisting of tetrahydropyran-2,5-diyl, 1, 3-dioxane-2.5 -diyl, tetrahydrofuran-2,5-diyl, Cylcobut-1, 3-diyl, piperidine-1, 4-diyl, thiophene-2,5-diyl and selen
  • one or more H atoms may be replaced by L, and / or one or more double bonds may be replaced by single bonds, and / or one or more CH groups may be replaced by N, n 0, 1, 2 or 3
  • Each Z 1 is independently -CO-O-, -O-CO-, -CH 2 O-,
  • n 2, 3 or 4, -O-, -CO-, -C (R y R z ) - , -CH 2 CF 2 -, -CF 2 CF 2 -, or a
  • L for each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF 5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms,
  • R 0 , R 00 are each independently H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which also one or more H atoms may be replaced by F,
  • M is -O-, -S-, -CH 2 -, -CHY - or -CY 1 Y 2 -, and
  • Y 1 , and Y 2 are each independently one of the above for R °
  • R c and R d are each, independently of one another, H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl,
  • the polymerizable group P a, b is a group suitable for a
  • Polymerization reaction such as radical or ionic chain polymerization, polyaddition or polycondensation, or for a polymer-analogous reaction, for example, the addition or
  • Condensation to a polymer backbone is suitable.
  • Preferred groups P a are selected from the group consisting of
  • Particularly preferred groups P ab are selected from the group consisting of:
  • Very particularly preferred groups P a, b are selected from
  • P ab are therefore selected from the group consisting of acrylate, methacrylate, fluoroacrylate, furthermore
  • Vinyloxy, chloroacrylate, oxetane and epoxy groups and among these, preferably an acrylate or methacrylate group.
  • Preferred spacer groups Sp a are selected from the formula Sp "-X", so that the radical P ⁇ -Sp 3 " 3 - of the formula P ⁇ -Sp" - '-, wherein Sp "alkylene having 1 to 20, preferably 1 to 12 carbon atoms means
  • CH 2 groups are each independently selected from -O-, -S-, -NH-, -N (R 0 ) -, -Si (R 00 R 000 ) -, -CO-, -CO-O-, -O-CO-, -O-CO-O-,
  • R 00 and R 000 are each independently H or alkyl of 1 to 12 carbon atoms
  • Y 2 and Y 3 are each independently H, F, Cl or CN.
  • X ' is preferably -O-, -S-CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -,
  • Typical spacer groups Sp are for example - (CH 2 ) p i-, - (CH 2 CH 2 O) q i - CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, -CH 2 CH 2 -NH -CH 2 CH 2 - or - (SiR 00 R 000 -O) p1 -, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 00 and R 000 are as defined above have.
  • Particularly preferred groups -Sp "-X" - are - (CH 2 ) p1 -, - (CH 2 ) p1 -O-,
  • Ethylenoxyethylene methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and
  • Particularly preferred monomers are the following:
  • P 1 and P 2 are each independently a polymerizable
  • Group as defined for formula II preferably an acrylate, methacrylate, fluoroacrylate, oxetane, vinyloxy or epoxy group,
  • Each of Sp 1 and Sp 2 independently represents a single bond or a spacer group, preferably with one of the meanings given above and below for Sp a , and particularly preferably - (CH 2 ) p i-, - (CH 2 ) p i-0- , - (CH 2 ) p 1 -CO-O- or - (CH 2 ) p 1 -O -CO-O-, wherein p 1 is an integer from 1 to 12, and wherein in the latter groups the linkage to the adjacent ring is via the O atom is carried out, it also being possible for one or more of the radicals P -Sp 1 - and P 2 -Sp 2 - to denote a radical R aa , with the proviso that at least one of the radicals P 1 -Sp 1 - and P 2 present -Sp 2 - not R aa means
  • R °, R 00 are each independently H or alkyl having 1 to 12 C atoms,
  • R y and R z are each independently H, F, CH 3 or CF 3 ,
  • Z 1 is -O-, -CO-, -C (R y R z ) -, or -CF 2 CF 2 -,
  • Z 2 and Z 3 are each independently of one another -CO-O-, -O-CO-, -CH 2 O-,
  • L for each occurrence equal or different F, Cl, CN, SCN,
  • SF 5 straight-chain or branched, optionally mono- or polyfluorinated, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or
  • L 'and L are each independently H, F or Cl,
  • the FK medium or the polymerizable contains
  • Component one or more compounds selected from the group of the formulas M1-M21, particularly preferably from the group of the formulas M2-M9, and very particularly preferably from the group of the formulas M2, M16, M17 and M18.
  • the FK medium or the polymerizable contains
  • Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably
  • Photopolymerization in particular UV photopolymerization. If appropriate, one or more initiators may also be added.
  • Suitable conditions for the polymerization are known in the art and described in the literature.
  • the commercially available photoinitiators Irgacure651®, Irgacure184®, Irgacure907®, Irgacure369®, or Darocurel 173® (Ciba AG) are suitable for the free-radical polymerization.
  • an initiator is used, its proportion is preferably 0.001 to 5 wt .-%, particularly preferably 0.001 to 1 wt .-%.
  • the polymerizable compounds according to the invention are also suitable for polymerization without initiator, which brings considerable advantages, such as lower material costs and in particular a lower contamination of the LC medium by possible residual amounts of the initiator or its degradation products.
  • the polymerization can thus be carried out without addition of an initiator.
  • the LC medium does not contain a polymerization initiator.
  • the polymerizable component or LC medium may also contain one or more stabilizers to prevent undesired spontaneous polymerization of the RMs, for example during storage or transportation. Suitable types and amounts of stabilizers are known to those skilled in the art and described in the literature. Particularly suitable are, for example, the commercially available stabilizers of the series Irganox® (Ciba AG), such as Irganox® 1076. If
  • Stabilizers are used, their proportion, based on the total amount of RMs or the polymerizable
  • Component preferably 10 - 10000 ppm, more preferably 50 - 500 ppm.
  • the LC media for use in the LC displays of the invention contain, in addition to the above-described polymerizable compounds and component (N), an LC mixture ("host mixture") containing one or more, preferably two or more low molecular weight (i.e.
  • the host mixture is any suitable dielectric negative FK mixture for use in conventional VA displays.
  • Suitable LC mixtures are known in the art and in the
  • liquid-crystalline medium which additionally contains one or more compounds
  • R 2A , R 2B and R 2C are each independently H, one
  • substituted alkyl radical having up to 15 C atoms, where in these radicals also one or more CH 2 groups is represented by -O-, -S-, - * -CsC-,
  • -CF2O-, -OCF2-, -OC-O- or -O-CO- may be replaced so that O atoms are not directly
  • L 1 -4 are each independently of one another F, Cl, CF 3 or CHF 2 , Z 2 and Z 2 'are each independently of one another single bond,
  • Z 2 may have the same or different meanings.
  • Z 2 and Z 2 ' may be the same or different
  • R 2 , R 2B and R 2C are each preferably alkyl having 1-6 C atoms, in particular CH 3 , C 2 H 5 , nC 3 H 7> nC 4 H 9 , nC 5 Hn.
  • Z 2 and Z 2 ' in the formulas IIIA and HIB are preferably each
  • Z 2 -C 2 H 4 -
  • (0) C v H 2v + i preferably denotes OC v H 2v + i, furthermore C v H 2v + i.
  • (0) C v H 2v + i is preferably
  • L 3 and L 4 are preferably in each case F.
  • alkyl and alkyl * each independently represent a straight-chain alkyl radical having 1-6 C atoms.
  • Particularly preferred mixtures according to the invention comprise one or more compounds of the formulas IIIA-2, IIIA-8, IIIA-14, IIIA-29, IIIA-35, IIIB-2, IIIB-11, IIIB-16 and IIIC-1.
  • the proportion of compounds of the formulas IIIA and / or HIB in the total mixture is preferably at least 20% by weight.
  • Particularly preferred media according to the invention contain
  • alkyl and alkyl * have the meanings given above, preferably in amounts of> 3% by weight, in particular> 5% by weight and particularly preferably from 5 to 25% by weight.
  • FK medium which additionally contains one or more compounds of the following formula: wherein the individual radicals have the following meaning
  • R 3 and R 4 are each independently alkyl with 1 to 12 C
  • the compounds of the formula ZK are preferably selected from the group consisting of the following sub-formulas:
  • alkyl and alkyl * each independently represent a straight-chain alkyl radical having 1-6 C atoms
  • alkenyl and alkenyl * represent a straight-chain alkenyl radical having 2-6 C atoms.
  • FK medium which additionally contains one or more compounds of the following formula: wherein the individual radicals on each occurrence are the same or
  • R 5 and R 6 are each independently one of the meanings given above for R, e 1 or 2.
  • the compounds of the formula DK are preferably selected from the group consisting of the following sub-formulas:
  • alkyl and alkyl * each independently of one another denote a straight-chain alkyl radical having 1-6 C atoms
  • alkenyl and alkenyl * each independently of one another denote a straight-chain alkenyl radical having 2-6 C atoms.
  • FK medium which additionally contains one or more compounds of the following formula:
  • R 1 and R 2 each independently of one another alkyl with 1 to 12 C
  • L 1 and L 2 are each independently of one another F, Cl, OCF 3 , CF 3 , CH 3 ,
  • both radicals L 1 and L 2 are F or one of the radicals L 1 and L 2 F and the other Cl.
  • the compounds of the formula LY are preferably selected from the group consisting of the following sub-formulas
  • R 1 has the meaning given above, alkyl
  • FK medium which additionally contains one or more compounds selected from the group consisting of the following formulas:
  • X is F.
  • FK medium which additionally contains one or more compounds selected from the group consisting of the following formulas: wherein R 5 has one of the meanings given above for R 1, alkyl C -6 alkyl, d is 0 or 1, and z and m each independently
  • R5 is in these compounds is particularly preferably Ci -6 alkyl or -alkoxy or C 2-6 - alkenyl containing d is preferably 1.
  • the salt is particularly preferably Ci -6 alkyl or -alkoxy or C 2-6 - alkenyl containing d is preferably 1.
  • FK medium according to the invention one or more compounds of the above formulas in amounts of> 5 wt.%.
  • LC medium which additionally contains one or more
  • Biphenyl compounds selected from the group consisting of the following formulas:
  • alkyl and alkyl * each independently
  • alkenyl and alkenyl * each independently represent a straight-chain alkenyl radical having 2-6 C atoms.
  • the proportion of the biphenyls of the formulas B1 to B3 in the LC mixture is preferably at least 3% by weight, in particular> 5% by weight.
  • the compounds of the formula B2 are particularly preferred.
  • the compounds of the formula B1 to B3 are preferably
  • alkyl * is an alkyl radical having 1-6 C atoms.
  • the medium according to the invention contains one or more compounds of the formulas B1a and / or B2c. h) LC medium, which additionally contains one or more
  • R 5 and R 6 each independently have one of the meanings given above for R 1 and in each case independently of one another in which L 5 is F or Cl, preferably F, and L 6 is F, Cl, OCF 3 , CF 3 , CH 3> CH 2 F or CHF 2 , preferably F.
  • the compounds of formula T are preferably selected from the group consisting of the following sub-formulas
  • R is a straight-chain alkyl or alkoxy radical having 1-7 C atoms
  • R * is a straight-chain alkenyl radical having 2-7 C atoms
  • R is methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy or pentoxy.
  • the LC medium according to the invention contains the terphenyls of the formulas T and their preferred sub-formulas preferably in an amount of 0.5-30% by weight, in particular of 1-20% by weight.
  • R preferably denotes alkyl, furthermore alkoxy in each case with 1-5 C atoms.
  • the terphenyls are in inventive
  • Preferred mixtures contain 2-20% by weight of one or more terphenyl compounds of the formula T, preferably selected from the group of the compounds T1 to T22.
  • FK medium which additionally contains one or more compounds selected from the group consisting of the following formulas: wherein R 1 and R 2 have the meanings given above for formula LY, and preferably each independently
  • straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms.
  • Preferred media contain one or more compounds selected from the formulas 01, 03 and 04.
  • k) LC medium which additionally contains one or more compounds of the following formula:
  • R 9 is H, CH 3 , C 2 H 5 or nC 3 H 7 , (F) is an optional fluorine substituent and q is 1, 2 or 3, and R 7 has one of the meanings given for R, preferably in amounts of> 3% by weight, in particular> 5% by weight, and very particularly preferably from 5 to 30% by weight.
  • Particularly preferred compounds of formula Fl are selected from the group consisting of the following sub-formulas: wherein R 7 is preferably straight-chain alkyl and R 9 is CH 3 , C 2 H 5 or nC 3 H 7 . Particularly preferred are the compounds of the formula FI1, FI2 and FI3. m) FK medium which additionally contains one or more compounds selected from the group consisting of the following formulas:
  • R 8 has the meaning given for R 1 for formula LY and alkyl is a straight-chain alkyl radical having 1-6 C atoms.
  • FK medium which additionally contains one or more compounds which have a tetrahydronaphthyl or naphthyl unit, for example the compounds selected from the group consisting of the following formulas:
  • R 10 and R 11 each independently have one of the meanings given for R 1 for formula LY, preferably straight-chain alkyl or alkoxy having 1 to 6 C atoms or
  • FK medium which additionally contains one or more difluorodibenzochromans and / or chromans of the following formulas:
  • R 10 and R 11 each independently of one another have the meaning given above for R 1 in formula LY, and c denotes 0 or 1, preferably in amounts of from 3 to 20% by weight,
  • Particularly preferred compounds of the formulas BC and CR are selected from the group consisting of the following sub-formulas:
  • alkyl and alkyl * each independently represent a straight-chain alkyl radical having 1-6 C atoms
  • Alkenyi and Alkenyi * each independently represent a straight-chain alkenyl radical having 2-6 C atoms.
  • R 1 and R 12 each independently of one another have the meanings given above for R 1 in formula LY, b is 0 or 1, LF and r is 1, 2 or 3.
  • Particularly preferred compounds of the formulas PH and BF are selected from the group consisting of the following sub-formulas: wherein R and R 'each independently represent a straight-chain alkyl or alkoxy radical having 1-7 C atoms.
  • the liquid-crystal mixture according to the invention is dielectrically negative with a dielectric anisotropy ( ⁇ ) of ⁇ -1.5.
  • the compounds of the formulas IIIA, HIB, INC, LY1-LY18, Y1-Y16, T1-T24, Fl, VK1-VK4, N1-N10, BC, CR, PH and BF are suitable as a dielectrically negative component.
  • the dielectrically negative compounds of the formulas are selected from the formulas IIIA, HIB and MIC.
  • the LC medium preferably has a ⁇ of -1.5 to -8.0, in particular of -2.5 to -6.0.
  • the values of the birefringence ⁇ in the liquid-crystal mixture are generally between 0.07 and 0.16, preferably between 0.08 and 0.12.
  • the rotational viscosity ⁇ at 20 ° C before the polymerization is preferably ⁇ 165 mPa-s, in particular ⁇ 140 mPa-s. The following abbreviations are used:
  • the LC media according to the invention contain one or more
  • Table B lists possible chiral dopants which can be added to the LC media according to the invention.
  • the LC media contain from 0 to 10% by weight, in particular from 0.01 to 5% by weight, particularly preferably from 0.1 to 3% by weight, of dopants,
  • Table C lists possible stabilizers which can be added to the LC media according to the invention.
  • n here denotes an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8, terminal methyl groups are not shown).
  • the LC media preferably contain 0 to 10% by weight, in particular 1 ppm to 5% by weight, more preferably 1 ppm to 1% by weight
  • the LC media contain one or more stabilizers selected from the group consisting of compounds of Table C.
  • Table D summarizes example compounds which can be used preferably as reactive compounds in the LC media according to the present invention.
  • the mesogenic media contain one or more compounds selected from the group of compounds of Table D.
  • the term “compounds”, also written as “compound (s)”, unless explicitly stated otherwise, means both one or more compounds. Conversely, the term “compound” generally also includes several compounds, as far as this is possible and not stated otherwise. The same applies to the Terms FK media and FK medium.
  • the term “component” in each case comprises one or more substances, compounds and / or particles.
  • threshold voltage refers to the capacitive threshold (V 0 ), also called the Freedericksz threshold, unless explicitly stated otherwise
  • the polymerizable compounds are polymerized in the display or test cell by irradiation with UVA light (usually 365 nm) of a defined intensity for a predetermined time, optionally with a voltage being applied to the display at the same time (usually 10 to 30 V AC, 1 kHz).
  • a mercury vapor lamp of 100 mW / cm 2 is used, the intensity is measured with a standard UV meter (manufactured by Ushio UNI meter) equipped with a bandpass filter at 320 nm.
  • PSS-1 PSS- [3- (2-aminoethyl) -amino] -propyl-heptaisobutyl substituted, CAS Registry # 444315-16-6) was obtained from Aldrich.
  • the structures PSS-1 to PSS-9 and RM-1 can be taken from the preceding description. example 1
  • a polymerizable compound (RM-1, 0.3 wt.%) And the diamine PSS-1 (0.25 wt.%) are added and homogenized.
  • test cells without preorientation layer ('alignment layer'):
  • the resulting mixture is filled into a test cell (without polyimide orientation layer, layer thickness d "5.2 ⁇ , double-sided ITO coating, without passivation layer).
  • the FK medium has a spontaneous homeotropic (vertical) orientation to the substrate surfaces. Without applying a voltage, the cell is irradiated for 6 min with UV light of intensity 100 mW / cm 2 . As a result, polymerization of the monomeric compound takes place. This orientation remains stable up to 70 ° C. In the temperature-stable range, the cell can be set by applying a
  • test cells without preorientation layer (alignment layer 1 ): The resulting mixture is filled into a test cell (without polyimide orientation layer, layer thickness d "5.2 ⁇ m, ITO coating on both sides, without passivation layer).
  • the FK medium has a spontaneous homeotropic (vertical) orientation to the substrate surfaces.
  • the resulting mixture is filled into a test cell (rubbed antiparallel, orientation layer VA polyimide, layer thickness d «4 pm). Without applying a voltage, the cell is irradiated for 6 min with UV light of intensity 100 mW / cm 2 . As a result, polymerization of the monomeric compound takes place.
  • a polymerizable compound (RM-1, 0.3 wt.%) And the diol PSS-3 (1, 0 wt.%) was added and homogenized.
  • the spontaneous homeotropic orientation is stable up to about 30 ° C and goes completely between 40-60 ° C in the planar orientation.
  • stabilized mixture is homotrophically aligned to> 50 ° C.
  • Example 2 Analogously to Example 2, the following compounds are used as component (N) and the LC medium is polymerized (Table 3).

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Abstract

L'invention concerne des fluides cristallins liquides et des écrans à cristaux liquides (écrans LCD) contenant ces fluides, à orientation homéotrope (verticale) et à stabilisation polymère du fluide cristallin liquide. Le fluide cristallin liquide contient des particules ayant une masse d'au moins 450 Da, fonctionnalisées par un radical actif organique polaire.
EP11735985.1A 2010-07-15 2011-06-29 Fluides cristallins liquides et écrans à base de cristaux liquides à orientation homéotrope à stabilisation polymère Active EP2593529B1 (fr)

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PCT/EP2011/003207 WO2012007107A1 (fr) 2010-07-15 2011-06-29 Fluides cristallins liquides et écrans à cristaux liquides à orientation homéotrope à stabilisation polymère

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